[2,3]-Sigmatropic rearrangements of 3-sulfinyl dihydropyrans: application to the syntheses of the cores of ent-dysiherbaine and deoxymalayamicin A.
The [2,3]-sigmatropic rearrangement of a variety of configurationally stable diastereomeric allylic sulfinyl dihydropyrans, produced by base-promoted cyclization of sulfinyl dienols, has been studied. In some cases, the efficient transformation of these substrates into dihydropyranols required an in-depth study of reaction conditions, with the preferred protocol relying on the use of DABCO in warm toluene. This methodology has been applied to the syntheses of the cores of ent-dysiherbaine and deoxymalayamicin A by means of efficient tethered aminohydroxylations.
Fernández de la Pradilla
Roberto
R
Instituto de Química Orgánica, CSIC, Juan de la Cierva, 3, 28006 Madrid, Spain. iqofp19@iqog.csic.es
Lwoff
Nadia
N
del Aguila
Miguel Angel
MA
Tortosa
Mariola
M
Viso
Alma
A
D000409:Alanine / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D006900:Hydroxylation; D011714:Pyrans / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D013454:Sulfoxides / Q000737:chemistry*; D014498:Uracil / Q000031:analogs & derivatives* / Q000138:chemical synthesis
D019086:Bridged Bicyclo Compounds, Heterocyclic; D011714:Pyrans; D013454:Sulfoxides; C534161:deoxymalayamicin A; C121741:dysiherbaine; D014498:Uracil; D000409:Alanine